EP1970411B1 - Härtbare zusammensetzung - Google Patents

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Publication number
EP1970411B1
EP1970411B1 EP06835121A EP06835121A EP1970411B1 EP 1970411 B1 EP1970411 B1 EP 1970411B1 EP 06835121 A EP06835121 A EP 06835121A EP 06835121 A EP06835121 A EP 06835121A EP 1970411 B1 EP1970411 B1 EP 1970411B1
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EP
European Patent Office
Prior art keywords
compound
polymer
group
curable composition
mass
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EP06835121A
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English (en)
French (fr)
Japanese (ja)
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EP1970411A1 (de
EP1970411A4 (de
Inventor
Yuuji Kimura
Tatsuhiro Futami
Hideaki Tanaka
Genichirou Enna
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AGC Inc
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Asahi Glass Co Ltd
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/336—Polymers modified by chemical after-treatment with organic compounds containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/548—Silicon-containing compounds containing sulfur

Definitions

  • the present invention relates to a curable composition.
  • a curable composition comprising a polymer having a hydrolysable silicon group at an end of a polyoxyalkylene chain (also called as a modified silicone polymer), undergoes moisture-curing to form a cured product which is excellent in rubber elasticity. Therefore, the curable composition is widely used as an adhesive, a coating agent or a sealing material. Especially, a curable composition made of a polymer having a methyldimethoxysilyl group at an end of a polyoxyalkylene chain, is widely accepted in a market as a sealing material due to its excellent elastic physical property (Patent Document 1).
  • a curable composition containing a polymer having a polyoxyalkylene chain and a trialkoxysilyl group has a high curing rate and a high crosslink density, whereby it is useful as a fast curable adhesive, coating agent or sealing material (Patent Document 2).
  • the curable composition may be a curable composition comprising a specific polymer having a polyoxyalkylene chain and a trialkoxysilyl group bonded to the polyoxyalkylene chain terminal through a -OCH 2 CH 2 CH 2 - or -SCH 2 CH 2 CH 2 - group, or a specific polymer having a polyoxyalkylene chain and a trialkoxysilyl group bonded to the polyoxyalkylene chain terminal through an urethane bond, and a compound having an amino group and an alkoxysilyl group (Patent Document 3).
  • Patent Document 1 JP-A-03-072527
  • Patent Document 2 JP-A-03-047825
  • Patent Document 2 JP-A-10-245482
  • the curable composition in Patent Document 2 had a high reactivity of a polymer having a polyoxyalkylene chain and a trialkoxysilyl group, whereby stability was low. Therefore, when the curable composition was to be stored, it was necessary to take a step to suppress an increase of viscosity of the curable composition by curing over time, and its handling was complex. The curable composition in Patent Document 3 was still not sufficient to satisfy both stability and fast curing properties.
  • a curable composition may be colored during the production, storage or curing reaction, by a reaction of the polymer or by a reaction with a trace component contained in the polymer, or with other additives such as an ultraviolet absorber or an antioxidant.
  • a composition comprising a polymer obtained by a urethane-forming reaction of a polymer having a polyoxyalkylene chain and a hydroxyl group with a compound having an isocyanate group.
  • a polymer is required to be as colorless as possible in order to improve the appearance of a cured product of a curable composition.
  • a curable composition comprising a specific polymer having a polyoxyalkylene chain and a trialkoxysilyl group, and a specific amount of a compound having a mercapto group and an alkoxysilyl group, has excellent fast curing properties and stability.
  • the present invention provides the following.
  • the curable composition of the present invention is useful as e.g. an adhesive for various applications.
  • the polymer having a polyoxyalkylene chain and a hydroxyl group and the polymer obtained by a urethane-forming reaction of a compound having an isocyanate group, are used, coloration does not occur during the storage or curing reaction, and the cured product will be excellent in appearance.
  • a group of the formula (1) is referred to as the group (1).
  • a number average molecular weight is referred to as Mn, a weight average molecular weight as Mw, and a molecular weight distribution as Mw/Mn.
  • the polymer in the present invention is a polymer having a polyoxyalkylene chain and the following group (1) : -Si(-X 1 ) 3 (1)
  • one type of the polymer (P) may be used alone, or two or more types of such polymer (P) may be used.
  • X 1 in the group (1) is preferably a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group or a hexyloxy group, and the methoxy group is particularly preferred.
  • Three X 1 s in the group (1) may be the same or different groups, and they are preferably the same groups.
  • the group (1) is preferably a group bonded to a polyoxyalkylene chain terminal through a divalent connecting group (preferably a divalent organic group having 1 to 20 carbon atoms).
  • the polyoxyalkylene chain in the polymer (P) comprises preferably oxyalkylene-polymerized units formed by ring-opening polymerization of a C 2-6 alkylene oxide, more preferably oxyalkylene-polymerized units formed by ring-opening polymerization of at least one alkylene oxide selected from a group consisting of ethylene oxide, propylene oxide, butylenes oxide and hexylene oxide, particularly preferably oxyalkylene-polymerized units formed by ring-opening polymerization of propylene oxide.
  • a polyoxyalkylene chain comprises two or more types of oxyalkylene-polymerized units
  • the arrangement of two or more types of the polymerized units may be in a block form or a random form.
  • Mn of the polymer (P) is preferably from 5,000 to 30,000, particularly preferably from 8,000 to 25,000. Further, Mw/Mn of the polymer (P) is preferably at most 3.0, more preferably at most 1.6, particularly preferably at most 1.5.
  • the polymer (P) is a polymer (P1) obtained by the following method 1. Also described is a polymer (P2) obtained by the following method 2 or a polymer (P3) obtained by the following method 3.
  • Method 1 A method to carry out a urethane-forming reaction of a polymer (pP) having a polyoxyalkylene chain and a hydroxyl group with a compound (U) having the group (1) and an isocyanate group.
  • Method 2 A method to carry out an addition reaction of a polymer (aP) having a polyoxyalkylene chain and an alkenyl group (hereinafter referred to as polymer (aP)) with a compound (M) having the group (1) and a mercapto group (hereinafter referred to as compound (M)).
  • Method 3 A method to carry out a hydrosilylation reaction of a polymer (aP) with a compound of a formula Si (-H) (-X 1 ) 3 .
  • the polymer (pP) in the method 1 is preferably a polymer (pP1) obtained by ring-opening polymerization of an alkylene oxide with a compound having an active hydrogen atom, in the presence of a double metal cyanide complex (zinc hexacyanocobaltate is preferred).
  • the double metal cyanide complex is preferably a double metal cyanide complex having an organic ligand.
  • the organic ligand is preferably an etheric type ligand or an alcohol type ligand.
  • etheric type ligand may be ethylene glycol dimethyl ether (glyme), diethylene glycol dimethyl ether (diglyme) and triethylene glycol dimethyl ether.
  • alcohol type ligand may be tert-butyl alcohol, n-butyl alcohol, sec-butyl alcohol, iso-butyl alcohol, tert-pentyl alcohol, iso-pentyl alcohol and ethylene glycol mono-tert-butyl ether.
  • the compound having an active hydrogen atom may be used alone or two or more such compounds may be used in combination as a mixture.
  • the compound having an active hydrogen atom is preferably an organic compound having an active hydrogen atom, more preferably a compound having a hydroxyl group or an amino group, particularly preferably a compound having from 1 to 4 hydroxyl groups.
  • organic compound having an active hydrogen atom may be ethylene glycol, propylene glycol, dipropylene glycol, butane diol, hexamethylene glycol, hydrogenated bisphenol A, neopentyl glycol, polybutadiene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, allyl alcohol, methallyl alcohol, glycerol, trimethylol methane, trimethylol propane and pentaerythritol.
  • polymer-form alcohol having Mn of from 300 to 1,500, selected from a group consisting of polyoxypropylene monool, polyoxypropylene diol, polyoxypropylene triol, polyoxyethylene monool, polyoxyethylene diol and polyoxyethylene triol.
  • the urethane-forming reaction with a compound (U) may be carried out after a double metal cyanide complex contained as a polymerization residue, is removed by purification, or the urethane-forming reaction with the compound (U) may be carried out without removing the double metal cyanide complex by purification.
  • the double metal cyanide complex functions not only as a catalyst for the ring-opening polymerization, but also as a catalyst for the urethane-forming reaction. Therefore, when the urethane-forming reaction of a polymer (pP1) with a compound (U) is carried out without removing a double metal cyanide complex contained in the polymer (pP1) as a polymerization residue, by purification, there is an effect such that the urethane-forming reaction efficiently proceeds.
  • the ratio of a total number of isocyanate groups of the compound (U) to a total number of hydroxyl groups in the polymer (pP1) (isocyanate groups/hydroxyl groups), is preferably from 0.80 to 1.05, particularly preferably from 0.85 to 1.00. In such a range, there will be an effect such that fast curing properties and storage stability of a curable composition will be remarkably improved.
  • the urethane-forming reaction may be carried out in the presence of a urethane-forming catalyst.
  • the urethane-forming catalyst is not particularly limited, and a metal catalyst such as an organic tin compound (such as dibutyltin diacetate, dibutyltin dilaurate or dioctyltin dilaurate) or a bismuth compound, or a basic catalyst such as an organic amine, is used.
  • the reaction temperature is at a level of preferably from 20 to 200°C, particularly preferably from 50 to 150°C.
  • the urethane-forming reaction is preferably carried out in an atmosphere of an inert gas (nitrogen gas is preferred).
  • the compound (U) is not particularly limited, but the following compound (U1) is preferred.
  • Q U is preferably a C 1-20 divalent hydrocarbon group, more preferably a C 1-10 alkylene group, and from the viewpoint of availability, a trimethylene group is particularly preferred.
  • X 1 is preferably a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group or a hexyloxy group, particularly preferably a methoxy group.
  • Specific examples for the compound (U) may be 1-isocyanatomethyltrimethoxysilane, 2-isocyanatoethyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatobutyltrimethoxysilane, 3-isocyanatopentyltrimethoxysilane, 1-isocyanatomethyltriethoxysilane, 2-isocyanatoethyltriethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-isocyanatobutyltriethoxysilane, 3-isocyanatopentyltriethoxysilane, 1-isocyanatopropyltrimethoxysilane and 1-isocyanatopropyltriethoxysilane.
  • the polymer (aP) is preferably a polymer (alP) having a polyoxyalkylene chain and an allyl group.
  • the polymer (alP) is preferably a polymer obtained by forming the polymer (pP1) into an alcoholate in the presence of an alkali metal halide, followed by a reaction with an allyl halide.
  • an alkali metal hydroxide sodium hydroxide or potassium hydroxide is preferred.
  • one type of the compound (S) may be used, or two or more types of the compound (S) may be used.
  • the compound (S) in the present invention is preferably the following compound (S1). Si(-X 2 ) m (Y 2 ) 3-m (-Q M -SH) (S1)
  • X 2 is preferably a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group or a hexyloxy group, particularly preferably a methoxy group.
  • n is preferably 2 or 3.
  • the plurality of X 2 in the compound (S) may be the same or different, and preferably the same.
  • Q M in the compound (S1) is preferably a C 1-20 divalent hydrocarbon, more preferably a C 1-10 alkylene group, particularly preferably a trimethylene group.
  • Y 2 in the compound (S1) is preferably a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group or a hexyl group, particularly preferably a methyl group.
  • Specific examples for the compound (S) may be 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltri-n-propoxysilane, 3-mercaptopropyltriisopropoxysilane, 3-mercaptopropyldimethoxyethoxysilane, 3-mercaptopropyl methoxydiethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldiethoxysilane, 3-mercaptopropylmethylmethoxyethoxysilane, 3-mercaptopropylmethyl-di-n-propoxysilane, 3-mercaptopropylmethyldiisopropoxysilane, 3-mercaptopropylethyldimethoxysilane, 3-mercaptopropylethyldiethoxysilane, 3-mercaptopropylethyl-di-n-propoxysilane, 3-mer
  • the curable composition of the present invention contains the compound (S) having both a mercapto group and the following group (2), whereby it has excellent fast curing properties and storage stability. Especially, it was unexpected that the curable composition containing the compound (S) of the present invention had effects for improving storage stability, which were not observed with a curable composition containing a compound having only a mercapto group. -Si(-X 2 ) m (-Y 2 ) 3-m (2)
  • the curable composition of the present invention contains from 0.01 to 0.50 part by mass of the compound (S) per 100 parts by mass of the polymer (P). Therefore, the curable composition of the present invention has excellent fast curing properties and storage stability.
  • the compound (S) suppresses a crosslinking reaction by a hydrolysis reaction with time of the polymer (P) by impurities (such as polymerization residues or unreacted components contained in the polymer (P)) in the curable composition.
  • the polymer (P) in the curable composition of the present invention is the polymer (P1) obtained by reacting the above polymer (pP1) and the compound (U) by an urethane-forming reaction, there is an effect such that storage stability of the curable composition will be remarkably improved.
  • a mercapto group of the compound (S) deactivates a double metal cyanide complex which may possibly be contained in the polymer (pP1) as a polymerization residue, and a crosslinking reaction by a hydrolysis reaction with time of the polymer (P1) is remarkably suppressed.
  • the polymer (P1) obtained by an urethane-forming reaction in the presence of an urethane catalyst it is considered that by deactivating the urethane catalyst which may possibly contain a mercapto group of the compound (S) as a residue, the crosslinking reaction by a hydrolysis reaction with time of the polymer (P1) is remarkably suppressed.
  • the curable composition of the present invention contains preferably from 0.02 to 0.50 part by mass, particularly preferably from 0.03 to 0.50 part by mass, of the compound (S) per 100 parts by mass of the polymer (P). In such a range, particularly excellent storage stability and fast curing properties will be imparted to the curable composition.
  • the curable composition by adding the compound (S) to the polymer (P), the curable composition may be obtained.
  • the antioxidant (T) is added and mixed to the polymer (P), and then, the compound (S) is added and mixed thereto to obtain the curable composition.
  • the antioxidant (T) is contained preferably from 0.01 to 10 parts by mass, particularly preferably from 0.1 to 1 part by mass, per 100 parts by mass of the polymer (P).
  • the antioxidant (T) before adding the compound (S), it is important that the antioxidant (T) is added and sufficiently mixed. If the antioxidant (T) is added after the compound (S) is added, or if the compound (S) and the antioxidant (T) are added simultaneously and mixed, there will be no effect to suppress an increase of chromaticity of the curable composition after the production.
  • the antioxidant (T) is not particularly limited but is preferably a hindered phenol or a hindered amine, particularly preferably a hindered phenol. Further, two or more such antioxidants may be contained.
  • Such may, specifically, be pentaerythritol, tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (manufactured by Ciba Specialty Chemicals Inc., tradename: IRGANOX 1010), 6-methylheptyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (manufactured by Ciba Specialty Chemicals Inc., tradename: IRGANOX 1135) or octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (manufactured by Ciba Specialty Chemicals Inc., tradename: IRGANOX 1076).
  • the chromaticity of the obtained curable composition is preferably less than 100.
  • the curable composition of the present invention preferably contains a compound of the following formula (V).
  • the curable composition of the present invention contains the compound (V), there will be an effect such that fast curing properties and storage stability will be improved.
  • n is preferably 3 or 4, more preferably 4.
  • X 3 is preferably a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group or a hexyloxy group, particularly preferably a methoxy group.
  • Three X 3 s in the compound (V) may be the same or different, preferably the same.
  • Y 3 is preferably a C 1-6 alkyl group or a C 1-6 alkenyl group, particularly preferably a methyl group, an ethyl group, a propyl group, a butyl group, a heptyl group, a hexyl group or a vinyl group.
  • the compound (V) may be methylmethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, phenyltriethoxysilane, methyltriacetoxysilane, vinyltrimethoxysilane, tetramethyl orthosilicate (tetramethoxysilane or methyl silicate), tetraethyl orthosilicate, tetrapropyl orthosilicate and tetrabutyl orthosilicate.
  • the compound (V) is contained preferably from 0.1 to 10 parts by mass, particularly preferably from 0.3 to 8 parts by mass, per 100 parts by mass of the polymer (P).
  • the curable composition of the present invention may further contain at least one additive selected from the group consisting of a curing catalyst, a filler, a plasticizer, an adhesion-promoting agent, a solvent, a dehydrating agent, a thixotropy-imparting agent, a stabilizing agent and a pigment.
  • at least one additive selected from the group consisting of a curing catalyst, a filler, a plasticizer, an adhesion-promoting agent, a solvent, a dehydrating agent, a thixotropy-imparting agent, a stabilizing agent and a pigment.
  • the curing catalyst is not particularly limited as long as it is a compound to catalyze the crosslinking reaction by a hydrolysis reaction of the group (1) of the polymer (P) with the group (2) of the compound (S).
  • Specific examples for the curing catalyst may be an organic tin compound, an organic metallic compound containing a metal other than tin, a metal organic alkoxide, a complex containing a metal other than tin, an organic amine and other catalysts.
  • organic metal compound containing a metal other than tin may be a calcium carboxylate, a zirconium carboxylate, an iron carboxylate, a vanadium carboxylate, a bismuth carboxylate such as bismuth tris-2-ethylhexoate, a lead carboxylate, a titanium carboxylate and a nickel carboxylate.
  • organic metal alkoxide may be a titanium alkoxide such as tetraisopropyl titanate, tetrabutyl titanate, tetramethyl titanate or tetra (2-ethyl hexyl titanate); an aluminum alkoxide such as aluminum isopropylate or mono-sec-butoxyaluminum diisopropylate; a zirconium alkoxide such as zirconium n-propylate or zirconium n-butylate; a titanium alkoxide such as titanium tetraacetylacetonate, titanium ethyl acetoacetate, titanium octylene glycolate and titanium lactate.
  • titanium alkoxide such as tetraisopropyl titanate, tetrabutyl titanate, tetramethyl titanate or tetra (2-ethyl hexyl titanate
  • aluminum alkoxide such as aluminum isopropylate or mono-sec
  • the complex containing a metal other than tin may be an aluminum chelate such as aluminum trisacetylacetonate, aluminum trisethyl acetoacetate or diisopropoxyaluminum ethyl acetate; or a zirconium chelate such as zirconium tetraacetylacetonate, zirconium bisacetylacetonate, a zirconium acetylacetonate bisethyl acetoacetate or zirconium acetate.
  • aluminum chelate such as aluminum trisacetylacetonate, aluminum trisethyl acetoacetate or diisopropoxyaluminum ethyl acetate
  • a zirconium chelate such as zirconium tetraacetylacetonate, zirconium bisacetylacetonate, a zirconium acetylacetonate bisethyl acetoacetate or zi
  • organic amine may be an aliphatic monoamine such as butyl amine, hexyl amine, octyl amine, decyl amine, lauryl amine or triethyl amine; an aliphatic diamine such as ethylene diamine or hexane diamine; an aliphatic polyamine such as diethylene triamine, triethylene tetramine or tetraethylene pentamine; a heterocyclic amine such as piperidine or piperazine; an aromatic amine such as metaphenylene diamine; an alkanol amine such as monoethanol amine, diethanol amine or triethanol amine; and various modified amines to be used for curing epoxy resins.
  • an aliphatic monoamine such as butyl amine, hexyl amine, octyl amine, decyl amine, lauryl amine or triethyl amine
  • an aliphatic diamine such as ethylene diamine or hex
  • catalysts may be phosphoric acid, p-toluene sulfonic acid and phthalic acid.
  • the curing catalyst is preferably the organic tin compound from the viewpoint of handling. From the viewpoint of fast curing properties, it is particularly preferably (n-C 4 H 9 ) 2 Sn(acac) 2 , (n-C 8 H 17 ) 2 Sn(acac) 2 , (n-C 4 H 9 ) 2 Sn(OC 8 H 17 )(acac), (n-C 4 H 9 ) 2 Sn(etac) 2 or (n-C 8 H 17 ) 2 Sn(etac) 2 .
  • the curing rate of the curable composition by properly selecting the curing catalyst.
  • the curing catalyst for example, it is possible to lower the curing rate of the curable composition of the present invention by selecting a low active catalyst as the curing catalyst.
  • a specific example for the low active catalyst may be a specific organic tin compound containing a sulfur atom in a ligand (such as tradename: UL-29 manufactured by Crompton Corporation and tradename: NEOSTANN U-860 manufactured by NITTO KASEI CO., LTD.).
  • the curable composition of the present invention may contain one curing catalyst, or it may contain two or more curing catalysts. When two or more curing catalysts are contained, it is preferred to contain an organic tin compound and an organic amine, since the curable composition of the present invention will then have excellent curing properties.
  • the curable composition of the present invention preferably contains from 0.001 to 10 parts by mass of the curing catalyst per 100 parts by mass of the polymer (P). In such a case, there will be effects such that the curing rate becomes high, and foaming during curing is suppressed, whereby durability of the curable composition will be improved.
  • specific examples for the filler may be calcium carbonate, silica, silicic anhydride, carbon black, magnesium carbonate, diatomaceous earth, clay, talc, titanium oxide, bentonite, ferric oxide, zinc oxide, charcoal, pulp, cotton chips, mica, walnut shell flour and rice hull flour.
  • the filler may be fine powder or fine hollow bodies (such as silica balloons, Shirasu balloons, glass balloons, or resin balloons).
  • the curable composition of the present invention may contain one filler or two or more fillers.
  • the calcium carbonate is preferably a calcium carbonate which is surface-treated by an aliphatic acid or a resin acid.
  • the calcium carbonate is preferably a colloidal calcium carbonate having an average particle size of at most 1 ⁇ m, a light calcium carbonate having an average particle size of from 1 to 3 ⁇ m or a heavy calcium carbonate having an average particle size of from 1 to 20 ⁇ m.
  • the curable composition of the present invention contains preferably at most 1000 parts by mass, particularly preferably from 50 to 250 parts by mass, of the filler, per 100 parts by mass of the polymer (P).
  • the plasticizer may, for example, be a phthalate such as dioctyl phthalate, dibutyl phthalate or butyl benzene phthalate; an aliphatic carboxylate such as dioctyl adipate, bis(2-methyl nonyl) succinate, dibutyl sebacate or butyl oleate; an alcohol ester such as pentaerythritol ester; a phosphate such as trioctyl phosphate or tricresyl phosphate; an epoxy type plasticizer such as epoxidized soybean oil, dioctyl 4,5-epoxyhexahydrophthalate or benzyl epoxystearate; a chlorinated paraffin; a polyester type plasticizer obtained by reacting a dibasic acid with a dihydric alcohol; a polyether type plasticizer such as polyoxypropylene glycol; a styrene type plasticizer such as poly- ⁇ -methyl s
  • the curable composition of the present invention contains preferably at most 1,000 parts by mass, particularly preferably from 1 to 100 parts by mass, of the plasticizer, per 100 parts by mass of the polymer (P).
  • adhesion-promoting agent in the present invention may be an organic silane coupling agent such as a silane having a (meta)acryloyloxy group, a silane having an amino group, a silane having an epoxy group or a silane having a carboxyl group; an organic metal coupling agent such as isopropyl tri(N-aminoethyl-aminoethyl)propyltrimethoxy titanate or 3-mercaptopropyltrimethoxy titanate; and an epoxy resin.
  • organic silane coupling agent such as a silane having a (meta)acryloyloxy group, a silane having an amino group, a silane having an epoxy group or a silane having a carboxyl group
  • an organic metal coupling agent such as isopropyl tri(N-aminoethyl-aminoethyl)propyltrimethoxy titanate or 3-mercaptopropyltrimethoxy titanate
  • an epoxy resin such as
  • silane having a (meta)acryloyloxy group may be 3-metacryloyloxy propyl trimethoxysilane, 3-acryloyloxy propyl trimethoxysilane and 3-metacryloyloxy propyl methyl dimethoxysilane.
  • silane having an amino group may be 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 3-aminopropyl methyl dimethoxysilane, N-(2-aminoethyl)-3-aminopropyl trimethoxysilane, N-(2-aminoethyl)-3-aminopropyl methyl dimethoxysilane, N-(2-aminoethyl)-3-aminopropyl triethoxysilane, 3-ureidopropyl triethoxysilane, N-(N-vinyl benzyl-2-aminoethyl)-3-aminopropyl trimethoxysilane and 3-anilinopropyl trimethoxysilane.
  • silane having an epoxy group may be 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyl methyl dimethoxysilane and 3-glycidyloxypropyltriethoxysilane.
  • silane having a carboxyl group may be 2-carboxyethyl triethoxysilane, 2-carboxyethylphenyl bis(2-methoxyethoxy)silane and N-(N-carboxylmethyl-2-aminoethyl)-3-aminopropyltrimethoxysilane.
  • reaction product obtained by reacting two or more silane coupling agents.
  • the reaction product may, for example, be a reaction product obtained by reacting the silane having an amino group with the silane having an epoxy group; a reaction product obtained by reacting the silane having an amino group with the silane having a (meta)acryloyloxy group; a reaction product obtained by reacting the silane having an epoxy group with the silane having a mercapto group; a reaction product obtained by reacting silanes having different mercapto groups.
  • the epoxy resin may be a bisphenol A-diglycidyl ether type epoxy resin, a bisphenol F-diglycidyl ether type epoxy resin, a tetrabromobisphenol A-glycidyl ether type epoxy resin, a novolak type epoxy resin, a hydrogenated bisphenol A type epoxy resin, a glycidyl ether type epoxy resin of bisphenol A-propylene oxide adduct, a glycidyl 4-glycidyloxy benzoate, a diglycidyl phthalate, a diglycidyl tetrahydrophthalate, a diglycidyl hexahydrophthalate, a diglycidylester type epoxy resin, a m-aminophenol type epoxy resin, a diaminodiphenyl methane type epoxy resin, an urethane modified epoxy resin, a N,N-diglycidyl aniline, a N,N-diglycidyl-o-to-to
  • the silane coupling agent is contained preferably from more than 0 to 30 parts by mass per 100 parts by mass of the polymer (P).
  • the epoxy resin is contained preferably at most 100 parts by mass per 100 parts by mass of the polymer (P).
  • the solvent may be an aliphatic hydrocarbon, an aromatic hydrocarbon, a halogenated hydrocarbon, an alcohol, a ketone, an ester, an ether, an ester alcohol, a ketone alcohol, an ether alcohol, a ketone ether, a ketone ester and an ester ether.
  • the alcohol is preferably a C 1-10 alkyl alcohol, more preferably methanol, ethanol, isopropanol, isopentyl alcohol or hexyl alcohol, particularly preferably methanol or ethanol.
  • the solvent is contained preferably at most 500 parts by mass per 100 arts by mass of the polymer (P).
  • specific examples for the dehydrating agent may be a trialkyl orthoformate such as trimethyl orthoformate, triethyl orthoformate, tripropyl orthoformate or tributyl orthoformate; and a trialkyl orthoacetate such as trimethyl orthoacetate, triethyl orthoacetate, tripropyl orthoacetate or tributyl orthoacetate.
  • the dehydrating agent is contained preferably from 0.001 to 30 parts by mass per 100 parts by mass of the polymer (P).
  • thixotropy-imparting agent may be a hydrogenated castor oil and an aliphatic amide.
  • a stabilizing agent other than the above antioxidant (T) may be used.
  • an ultraviolet absorber or a light stabilizer may be mentioned.
  • the stabilizer may be an age resistor of a benzotriazole type, a benzophenol type, a benzoate type, a cyanoacrylate type, an acrylate type, a phosphorus type and a sulfur type.
  • the pigment may be an inorganic pigment such as iron oxide, chrome oxide or titanium oxide; and an organic pigment such as phthalocyanine blue or phthalocyanine green.
  • the method for producing the curable composition of the present invention is not particularly limited. For example, there is a method wherein from 0.01 to 0.50 parts by mass of the compound (S) is mixed with 100 parts by mass of the polymer (P).
  • the order of blending such other components is not particularly limited, but it is preferred to mix the curable composition of the present invention with such other components except for the curing catalyst, and then mixing the curing catalyst thereto.
  • the curing method for the curable composition of the present invention is not particularly limited, but it is preferred to use a curing method for a one-pack type curable composition wherein the curable composition of the present invention is mixed with desired other components, sealed and stored, and at the time of its use, the mixture is cured by moisture in the air, or a curing method for a two-pack type curable composition wherein the curable composition of the present invention and the desired other components are mixed and properly cured when they are to be used.
  • the curable composition of the present invention is capable of forming a cured product having high curing properties and storage stability and having good mechanical properties.
  • the curable composition of the present invention is useful as a sealant for building, a waterproof material, an adhesive, a sealing material or a coating agent. It is particularly useful as an adhesive.
  • a preferred application for using the adhesive made of the curable composition of the present invention is a one-pack type curable adhesive wherein the curable composition of the present invention is mixed with desired other components, sealed and stored, and at the time of its use, the adhesive is cured by moisture in the air, or a two-pack type curable adhesive wherein the curable composition of the present invention and the desired other components are mixed and cured when they are to be used.
  • NCO/OH The ratio of the total amount of isocyanate groups to the total amount of hydroxyl groups of the polymer
  • the molecular weight and the molecular weight distribution were measured by Gel permeation chromatography (standard: polystyrene).
  • the hydroxyl value (mg ⁇ KOH/g) was measured in accordance with JIS K1557.
  • the analysis by a Fourier transform infrared spectrophotometer was carried out by a transmission method using a KBr plate.
  • PREPARATION EXAMPLE Preparation Example for Polymer (P) PREPARATION EXAMPLE 1: Preparation Example for Polymer (P-1)
  • the viscosity increase was measured by using a B-type viscometer (rotor used: No. 6, measurement temperature: 25°C, rotational speed: 10.5 rpm).
  • the initial viscosity (Pa ⁇ s) represents a viscosity of a curable composition immediately after it was prepared
  • the later viscosity (Pa ⁇ s) represents a viscosity of a curable composition after it was stored for 1 week at 80°C
  • the viscosity increase represents a % value of (latter viscosity - initial viscosity)/initial viscosity.
  • the results are shown in Table 3.
  • Blended compositions 2 to 9 and comparative blended compositions 1 to 4 were obtained in the same manner, except that the curable compositions 2 to 9 or the comparative curable compositions 1 to 4 were used instead of the curable composition 1.
  • a tensile shearing test was carried out with respect to each of the blended compositions 1 to 9 and the comparative blended compositions 1 to 4.
  • the tensile shearing test was carried out in accordance with JIS K6850. Specifically, by using a blended composition, two anodized aluminum plates were bonded to face each other through a spacer, and it was cured and aged for 7 days at 23°C under a humidity of 50%. Then, the spacer was removed, followed by curing for 7 days at 50°C under a humidity of 50%.
  • the 50% tensile stress (N/mm 2 ) (hereinafter referred to as M50), the tensile stress (N/mm 2 ) (hereinafter referred to as Tmax), and the elongation (%) (hereinafter referred to as E) under the maximum stress, were measured by using a TENSILON testing instrument (manufactured by A & D Co. Ltd, tradename: series RTA-1T). The results are shown in Table 3.
  • Blended composition (4) 20.2 20.6 2 73 0.32 1.09 471 Ex. 5 Blended composition (5) 7.8 7.9 1 60 0.82 1.28 116 Ex. 6 Blended composition (6) 19.0 19.2 1 75 0.26 0.95 502 Ex. 7 Blended composition (7) 18.6 18.6 0 72 0.32 1.09 478 Ex. 8 Blended composition (8) 20.0 25.1 26 74 0.41 1.31 266 EX. 9 Blended composition 18.5 25.0 35 77 0.18 0.78 562 Comp. Ex. 1 Comparative blended composition (1) 20.5 32.0 56 70 0.30 1.14 477 Comp. Ex. 2 Comparative blended composition (2) 20.4 20.3 0 168 0.36 1.19 471 Comp. Ex. 3 Comparative blended composition (3) 7.7 12.2 58 57 0.80 1.26 116 Comp. Ex.4 Comparative blended composition (4) 20.6 25.0 21 101 0.20 0.93 532
  • the curable compositions 1 to 9 containing specific amounts of the polymer (P) and the compound (S) have a low viscosity increase and excellent storage stability. Further, it is evident that when the polymer (P-1), the polymer (P-2) or the polymer (P-3) was used as the polymer (P) in the above curable composition, the curable composition is particularly excellent in storage stability.
  • blended compositions prepared from the above curable compositions have a short tacking free time and fast curability, and their 50% tensile stress, tensile stress, and elongation under the maximum stress are high, whereby cured products having excellent mechanical strength are formed.
  • curable composition 10 has excellent appearance.
  • the curable composition of the present invention is a curable composition which is capable of forming a cured product having excellent mechanical strength, and which has fast curing properties, excellent storage stability and also excellent appearance.
  • the curable composition of the present invention is useful as an adhesive to be used in the field of e.g. a sealing material (such as an elastic sealing material sealant for building or a sealing material for multilayer glass), a sealant (such a sealant for rust prevention ⁇ waterproof of glass ends or a sealant for a rear side of a solar cell), or an electrical insulating material (an insulating coating for wire ⁇ cable).
  • a sealing material such as an elastic sealing material sealant for building or a sealing material for multilayer glass
  • a sealant such a sealant for rust prevention ⁇ waterproof of glass ends or a sealant for a rear side of a solar cell
  • an electrical insulating material an insulating coating for wire ⁇ cable
  • the curable composition of the present invention may be used as an adhesive, a coating material, a film material, a gasket material or a casting material.

Claims (8)

  1. Härtbare Zusammensetzung umfassend:
    ein Polymer (P) mit einer Polyoxyalkylen-Kette und einer Gruppe der folgenden Formel (1), wobei das Polymer (P) erhalten wird durch eine Urethan-bildende Reaktion eines Polymers (pP), das eine Polyoxyalkylen-Kette und eine Hydroxygruppe aufweist, mit einer Verbindung (U), die eine Gruppe der folgenden Formel (1) und eine Isocyanatgruppe aufweist, und wobei in der Urethan-bildenden Reaktion das Verhältnis der Gesamtzahl an Isocyanatgruppen in der Verbindung (U) zur Gesamtzahl an Hydroxygruppen im Polymer (pP) 0,80 bis 1,05 beträgt, und
    eine Verbindung (S), die eine Mercaptogruppe und eine Gruppe der folgenden Formel (2) aufweist, und
    die 0,01 bis 0,50 Gewichtsteile der Verbindung (S) pro 100 Gewichtsteile Polymer (P) enthält:

            -Si(-X1)3     (1)

            -Si(-X2)m(-Y2)3-m     (2)

    wobei die Symbole die folgenden Bedeutungen haben:
    X1 und X2: jedes steht unabhängig voneinander für eine C1-6 Alkoxygruppe,
    Y2: eine C1-6 Alkylgruppe und
    m: 1, 2 oder 3.
  2. Die härtbare Zusammensetzung gemäß Anspruch 1, wobei die Verbindung (U) eine Verbindung der folgenden Formel (U1) ist:

            Si(-X1)3(-QU-NCO)     (U1)

    wobei die Symbole die folgenden Bedeutungen haben:
    X1: eine C1-6 Alkoxygruppe und
    QU: eine C1-20 divalente organische Gruppe.
  3. Die härtbare Zusammensetzung gemäß einem der Ansprüche 1 oder 2, wobei die Verbindung (S) eine Verbindung der folgenden Formel (S1) ist:

            Si(-X2)m(-Y2)3-m(-QM-SH)     (S1)

    wobei die Symbole die folgenden Bedeutungen haben:
    X2: eine C1-6 Alkoxygruppe,
    Y2: eine C1-6 Alkylgruppe,
    m: 1, 2 or 3 und
    QM: eine C1-20 divalente organische Gruppe.
  4. Die härtbare Zusammensetzung gemäß einem der Ansprüche 1 bis 3, die ferner eine Verbindung der folgenden Formel (V) enthält:

            Si(-X3)n(-Y3)4-n     (V)

    wobei die Symbole die folgenden Bedeutungen haben:
    X3: eine C1-6 Alkoxygruppe,
    Y3: eine C1-6 Kohlenwasserstoffgruppe und
    n: 1, 2, 3 oder 4.
  5. Die härtbare Zusammensetzung gemäß einem der Ansprüche 1 bis 4, die ferner ein Antioxidans (T) enthält und wobei die Zusammensetzung 0,01 bis 0,50 Gewichtsteile der Verbindung (S) und 0,01 bis 10 Gewichtsteile des Antioxidans (T) pro 100 Gewichtsteilen Polymer (P) enthält.
  6. Die härtbare Zusammensetzung gemäß einem der Ansprüche 1 bis 4, die durch Zugeben und Mischen eines Antioxidans (T) zum Polymer (P) erhalten wird, gefolgt von Zugeben und Mischen der Verbindung (S), und die 0,01 bis 0,50 Gewichtsteile der Verbindung (S) und 0,01 bis 10 Gewichtsteile des Antioxidans (T) pro 100 Gewichtsteile Polymer (P) enthält.
  7. Die härtbare Zusammensetzung gemäß Anspruch 5 oder 6, die eine Chromatizität von wenidger als 100 aufweist.
  8. Klebstoff oder Abdichtmaterial unter Verwendung der härtbaren Zusammensetzung gemäß einem der Ansprüche 1 bis 7.
EP06835121A 2005-12-26 2006-12-22 Härtbare zusammensetzung Not-in-force EP1970411B1 (de)

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CN101405315B (zh) * 2006-01-26 2011-04-13 Sika技术股份公司 具有良好的粘附性的含有硅烷官能的聚合物的湿固化组合物
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ES2397861T3 (es) * 2006-08-16 2013-03-11 Asahi Glass Company, Limited Composición polimérica
DE502008000156D1 (de) * 2008-03-05 2009-12-03 Sika Technology Ag Zusammensetzung mit verbesserter Haftung auf porösen Substraten
JP5456267B2 (ja) * 2008-03-13 2014-03-26 モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社 室温硬化性ポリマー組成物およびその製造方法
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CN101346431A (zh) 2009-01-14
JPWO2007074736A1 (ja) 2009-06-04
EP1970411A1 (de) 2008-09-17
US7709588B2 (en) 2010-05-04
US20080269392A1 (en) 2008-10-30
TW200734399A (en) 2007-09-16
EP1970411A4 (de) 2011-01-05
KR101320796B1 (ko) 2013-10-22

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